CN105293774A - Method for increasing recovery rate of precious metals in waste liquid - Google Patents
Method for increasing recovery rate of precious metals in waste liquid Download PDFInfo
- Publication number
- CN105293774A CN105293774A CN201510797339.3A CN201510797339A CN105293774A CN 105293774 A CN105293774 A CN 105293774A CN 201510797339 A CN201510797339 A CN 201510797339A CN 105293774 A CN105293774 A CN 105293774A
- Authority
- CN
- China
- Prior art keywords
- waste liquid
- precious metal
- recovery
- slag
- precious metals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for increasing recovery rate of precious metals in waste liquid. The method is characterized in that characteristic of large volume flocculent precipitates generated with a flocculating agent under weak alkaline condition is used, granular metal precipitates growth is promoted, floated hydrolysis particles and various suspended colloid particles in the waste liquid can be absorbed simultaneously, large granular precipitates are generated, then precious metals are recovered, metal precipitates re-dissolution phenomenon due to heat release of an alkalescence reagent in the prior art can be improved, precious metals recovery rate is increased; then a primary neutralization solution is discharged to outside, slurrying of a primary neutralization slag is carried out, strong acid is added for immersing the primary neutralization slag to gather base metals, then secondary alkali neutralization is carried out on acid immersion liquid for recovering the base metals, the precious metals from the acid-leached residues can be recovered, the obtain a secondary neutralization slag is added into a copper nickel system for comprehensive processing, a secondary neutralization solution is discharged to outside, and the precious metals and base metals are effectively separated. The content of the precious metals and the base metals in a discharge liquid can reach a national standard (GB25467-2010: copper, nickel, cobalt industrial pollutant discharge standard).
Description
Technical field
The present invention relates to metallurgical technology technology, specifically a kind of method improving the precious metal rate of recovery in waste liquid.
Background technology
Domestic large-scale smeltery produces the method that precious metal adopts wet method or pyrogenic process-wet method to combine usually, but these two kinds of methods all can produce the waste liquid containing heavy metals such as a small amount of precious metal and high density copper, nickel and arsenic, directly being discharged if do not processed, while the loss causing precious metal and the wasting of resources, also will certainly cause severe contamination to the water of enterprise's periphery and soil.These are contained to the waste liquid of precious metal, conventional treatment process mainly contains moderate water-cut stage, ferrite process and sulfuration method.In and lime precipitation application the most general, its cost is low, technique simple, but there is the shortcomings such as processing rate is low, precious metal is difficult to enrichment, the quantity of slag is large.Ferrite process and sulfuration method processing efficiency are higher than neutralisation, but these two kinds of method complicated operations, wherein sulfuration method easily produces the toxic and harmfuls such as hydrogen sulfide, and it is low to the rate of recovery of Noble Metal Rhodium, iridium, and the requirement of ferrite process to reaction conditions tolerance range is higher, the waste liquid heavy metal removing rate after process is difficult to the standard meeting discharge.Amid all these factors, neutralizer alkaline precipitation is being widely used containing in the process of precious metal waste liquid.
The operating process of the method is: the precipitin reaction utilizing metal ion, pH is regulated to become weakly alkaline, impel most of metal ion or complex ion generation precipitation to stay in slag the waste liquid liquid caustic soda containing precious metal ion, repeat said process, precious metal removes by first time as much as possible, and the heavy metal ion such as the copper in solution, nickel are reduced to discharging standards by second time.
But but there are the following problems for aforesaid method: (1) liquid caustic soda releases heat in the process added, a small amount of precious metal precipitation occurs returning molten phenomenon, and the rate of recovery of precious metal is reduced, and need increase the process of waste liquid cooling, affects production schedule; (2) add deposit seeds that liquid caustic soda precipitation metal generates and viscosity comparatively large, later stage speed of filter pressing is slow, and easily blocks filter bag, makes that operation efficiency reduces, cost increases.
Summary of the invention
The object of the invention is the deficiency in order to overcome above technology, a kind of novel method that effectively can improve the precious metal rate of recovery in waste liquid is provided.
The present invention improves the method for the precious metal rate of recovery in waste liquid, be first 8 ~ 10 by the waste liquid alkaline reagents adjust ph containing precious metal, after leaving standstill 30 ~ 40min generation small-particle precipitation, add the flocculation agent of 0.5 ~ 0.6g/L, utilize this flocculation agent under weak basic condition, generate the characteristic of large volume flocks, promote the growth of small-particle precipitated metal, adsorb the colloidal solid of floating hydrolyze granular and various suspension in waste liquid simultaneously, precious metal is reclaimed after generating macrobead sedimentable matter, improve the precipitated metal caused because of alkaline reagents heat release in prior art and return molten phenomenon, improve the rate of recovery of precious metal.A neutralizer is arranged outward by said process, but due in once and the quantity of slag of slag large, various total metal content is high, the Purity of Noble Metals that impact is reclaimed, therefore also needs in once and the pulp of slag pure water, then under the acidic conditions of pH=2 ~ 3 acidleach with enrichment base metal, pickling liquor is carried out in secondary alkali and is reclaimed base metal, acid leaching residue is for reclaiming precious metal, and the Two-step neutralization slag obtained adds copper nickel system and carries out comprehensive treating process, and Two-step neutralization liquid is arranged outward.
Above-mentioned alkaline reagents is the one in liquid caustic soda, calcium hydroxide or potassium hydroxide, and liquid caustic soda concentration is 10% ~ 30%.
Flocculation agent is the one in bodied ferric sulfate, iron trichloride or polyacrylamide.
Once and slag by pure water pulp time, liquid-solid volume ratio is 6:1 ~ 7:1.
Strong acid is the one in the hydrochloric acid of the sulfuric acid of 18.4mol/L, 9.5mol/L.
Acid solution after enrichment to carry out in secondary alkali and time pH value be still 8 ~ 10, the reaction times is 40 ~ 50min.
The present invention is compared to prior art, there is following beneficial effect: (1) the present invention utilizes flocculation agent under weak basic condition, generate the characteristic of large volume flocks, promote the growth of small-particle precipitated metal, adsorb the colloidal solid of floating hydrolyze granular and various suspension in waste liquid simultaneously, precious metal is reclaimed after generating macrobead sedimentable matter, improve the precipitated metal caused because of alkaline reagents heat release in prior art and return molten phenomenon, improve the rate of recovery of precious metal; Then a neutralizer is arranged outward, once and slag after pulp, acidleach enrichment base metal, base metal is reclaimed in the immersion liquid of secondary alkali neutralizing acid, and precious metal is reclaimed from acid leaching residue, the Two-step neutralization slag obtained adds copper nickel system and carries out comprehensive treating process, Two-step neutralization liquid is arranged outward, achieves effective separation that is expensive, base metal, and makes the content of precious metal and heavy metal in relief liquor all reach national standard (GB25467-2010: copper, nickel, cobalt emission of industrial pollutants standard).
(2) complex compound sediment generated when reclaiming precious metal in the present invention is floss, not easily blocks filter bag, and filtration velocity is fast, is conducive to improving production schedule, can be applicable widely in precious metal field of reclaiming.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Embodiment
Below in conjunction with the drawings and specific embodiments, invention is described in further detail.
Embodiment 1
Measure the acidity of waste liquid, add liquid caustic soda and once neutralize, adjust ph is 8, leave standstill 30min, wait have small-particle precipitate generate after add bodied ferric sulfate 0.5g/L, press filtration, obtain a neutralizer and once in and slag; Then a neutralizer is arranged outward, once, add vitriol lixiviation with slag with after the pure water pulp of 6 times of volumes, regulate endpoint pH to be 2, filter after stirring 10min, obtain acid leaching residue and pickling liquor; Acid leaching residue is for reclaiming precious metal, and Two-step neutralization recovery base metal is wherein carried out in pickling liquor, and being specially adjust ph is 8, stirs 40min, and the Two-step neutralization slag obtained after filtration is added copper nickel system and carries out comprehensive treating process, Two-step neutralization liquid is arranged outward.In whole removal process, 1L waste liquid produce 500g once in and slag, 15g acid leaching residue, recovery obtains 0.1g precious metal, obtain 450g Two-step neutralization slag, in a neutralizer and Two-step neutralization liquid, precious metal and heavy metal content are all lower than 0.0005g/L, and be up to state standards GB25467-2010.Use method in the present embodiment to reclaim various metal content in the waste liquid of front and back to contrast in table 1:
metal content detected result (mg/L) in waste liquid before and after table 1 reclaims
Embodiment 2
Measure the acidity of waste liquid, add calcium hydroxide and once neutralize, adjust ph is 8.5, leave standstill 35min, wait have small-particle precipitate generate after add bodied ferric sulfate 0.55g/L, press filtration, obtain a neutralizer and once in and slag; A neutralizer is arranged outward, once, adds vitriol lixiviation with slag with after the pure water pulp of 6 times of volumes, regulate endpoint pH to be 2.5, filter after stirring 15min, obtain acid leaching residue and pickling liquor; Acid leaching residue is for reclaiming precious metal, and Two-step neutralization recovery base metal is wherein carried out in pickling liquor, and being specially adjust ph is 8.5, stirs 45min, and the Two-step neutralization slag obtained after filtration is added copper nickel system and processes, Two-step neutralization liquid is arranged outward.In whole removal process, 1L waste liquid produce 520g once in and slag, 17g acid leaching residue, recovery obtains about 0.12g precious metal, obtain 455g Two-step neutralization slag, in a neutralizer and Two-step neutralization liquid, precious metal and heavy metal content are all lower than 0.0005g/L, and be up to state standards GB25467-2010.Use method in the present embodiment to reclaim various metal content in the waste liquid of front and back to contrast in table 2:
metal content detected result (mg/L) in waste liquid before and after table 2 reclaims
Embodiment 3
Measure the acidity of waste liquid, add calcium hydroxide and once neutralize, adjust ph is 9, leave standstill 35min, wait have small-particle precipitate generate after add iron trichloride 0.55g/L, press filtration, obtain a neutralizer and once in and slag; Add hydrochloric acid acidleach with slag with after the pure water pulp of 7 times of volumes once, regulate endpoint pH to be 2.5, filter after stirring 15min, obtain acid leaching residue and pickling liquor; Acid leaching residue is for reclaiming precious metal, and Two-step neutralization recovery base metal is wherein carried out in pickling liquor, and being specially adjust ph is 9.5, stirs 45min, and the Two-step neutralization slag obtained after filtration is added copper nickel system and processes, Two-step neutralization liquid is arranged outward.In whole removal process, 1L waste liquid produce 550g once in and slag, 15g acid leaching residue, recovery obtains 0.1g precious metal, obtain 450g Two-step neutralization slag, in a neutralizer and Two-step neutralization liquid, precious metal and heavy metal content are lower than 0.0005g/L, and be up to state standards GB25467-2010.The present embodiment is used to reclaim front and back metal ions in waste liquor content balance in table 3:
metal content detected result (mg/L) in waste liquid before and after table 3 reclaims
Embodiment 4
Measure the acidity of waste liquid, add calcium hydroxide and once neutralize, adjust ph is 10, leave standstill 40min, wait have small-particle precipitate generate after add polyacrylamide 0.6g/L, press filtration, obtain a neutralizer and once in and slag; A neutralizer is arranged outward, once, adds vitriol lixiviation with slag with after the pure water pulp of 7 times amount, regulate endpoint pH to be 3, filter after stirring 20min, obtain acid leaching residue and pickling liquor; Acid leaching residue is for reclaiming precious metal, and Two-step neutralization recovery base metal is wherein carried out in pickling liquor, and being specially adjust ph is 10, stirs 50min, and the Two-step neutralization slag obtained after filtration is entered copper nickel system and processes, Two-step neutralization liquid is arranged outward.In whole removal process, 1L waste liquid produce 700g once in and slag, 15g acid leaching residue, recovery obtains 0.1g precious metal, obtain 680g Two-step neutralization slag, in a neutralizer and Two-step neutralization liquid, precious metal and heavy metal content are all lower than 0.0005g/L, and be up to state standards GB25467-2010.Use method in the present embodiment to reclaim various metal content in the waste liquid of front and back to contrast in table 4:
metal content detected result (mg/L) in waste liquid before and after table 4 reclaims
Claims (8)
1. improve a method for the precious metal rate of recovery in waste liquid, it is characterized in that being undertaken by following processing step:
(1) once neutralize to containing adding alkaline reagents in the waste liquid of precious metal, adjust ph is 8 ~ 10, leaves standstill 30-40min, and precipitate the flocculation agent adding 0.5 ~ 0.6g/L after generating wait there being small-particle, press filtration, arranges a neutralizer outward;
(2) will once in and slag with liquid-solid volume ratio 6:1 ~ 7:1 pure water pulp, add strong acid acidleach, endpoint pH is 2 ~ 3, and stir after 10 ~ 20min and filter, acid leaching residue is for reclaiming precious metal.
2. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 1, it is characterized in that: the method also comprises step (3): carry out Two-step neutralization to pickling liquor with alkaline reagents, pH is regulated to be 8 ~ 10, reaction times 40 ~ 50min, the rear Two-step neutralization slag of filtration adds copper nickel system and processes, and Two-step neutralization liquid is arranged outward.
3. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 1, is characterized in that: described step (1) neutral and alkali reagent is the one in liquid caustic soda, calcium hydroxide or potassium hydroxide.
4. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 2, is characterized in that: described step (3) neutral and alkali reagent is the one in liquid caustic soda, calcium hydroxide or potassium hydroxide.
5. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 3 or 4, is characterized in that: described step (1) or (3) middle liquid paper mill wastewater are 10% ~ 30%.
6. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 1, is characterized in that: in described step (1), flocculation agent is the one in bodied ferric sulfate, iron trichloride or polyacrylamide.
7. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 1, is characterized in that: in described step (2), strong acid is the one in sulfuric acid, hydrochloric acid.
8. a kind of method improving the precious metal rate of recovery in waste liquid according to claim 7, is characterized in that: the concentration of described sulfuric acid, hydrochloric acid is respectively 18.4mol/L and 9.5mol/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510797339.3A CN105293774A (en) | 2015-11-18 | 2015-11-18 | Method for increasing recovery rate of precious metals in waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510797339.3A CN105293774A (en) | 2015-11-18 | 2015-11-18 | Method for increasing recovery rate of precious metals in waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105293774A true CN105293774A (en) | 2016-02-03 |
Family
ID=55191717
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510797339.3A Pending CN105293774A (en) | 2015-11-18 | 2015-11-18 | Method for increasing recovery rate of precious metals in waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105293774A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760488A (en) * | 2020-12-28 | 2021-05-07 | 格林美股份有限公司 | Separation method for iron in precious solution leached by automobile exhaust waste catalyst |
| CN114477507A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Treatment method and application of noble metal-containing production wastewater of vinyl acetate catalyst |
| CN114735842A (en) * | 2022-03-07 | 2022-07-12 | 金川集团股份有限公司 | Method for removing heavy metals from ammonia-containing wastewater |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718784A (en) * | 2005-07-07 | 2006-01-11 | 孙涛 | Method of recovery copper, nickel and noble metal in waste water and slag by combined technology of wet method and fire method |
| CN101096276A (en) * | 2007-06-22 | 2008-01-02 | 陈启松 | Method for abstracting chromium and nickel salt for stainless steel acid-washing wastewater |
| CN102218337A (en) * | 2010-04-16 | 2011-10-19 | 四川久源环保科技发展有限公司 | Oil and gas field wastewater treatment catalyst and oil and gas field wastewater treatment method |
| CN103613182A (en) * | 2013-12-10 | 2014-03-05 | 成应向 | Heavy-metal high flocculant and application thereof |
| CN103819023A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Treatment and recycling method of industrial wastewater containing a plurality of heavy metal ions |
| CN104341056A (en) * | 2013-07-24 | 2015-02-11 | 上海派特贵金属环保科技有限公司 | A method and a treatment trough for treating waste liquid of a precious-metal recovery process |
-
2015
- 2015-11-18 CN CN201510797339.3A patent/CN105293774A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1718784A (en) * | 2005-07-07 | 2006-01-11 | 孙涛 | Method of recovery copper, nickel and noble metal in waste water and slag by combined technology of wet method and fire method |
| CN101096276A (en) * | 2007-06-22 | 2008-01-02 | 陈启松 | Method for abstracting chromium and nickel salt for stainless steel acid-washing wastewater |
| CN102218337A (en) * | 2010-04-16 | 2011-10-19 | 四川久源环保科技发展有限公司 | Oil and gas field wastewater treatment catalyst and oil and gas field wastewater treatment method |
| CN104341056A (en) * | 2013-07-24 | 2015-02-11 | 上海派特贵金属环保科技有限公司 | A method and a treatment trough for treating waste liquid of a precious-metal recovery process |
| CN103613182A (en) * | 2013-12-10 | 2014-03-05 | 成应向 | Heavy-metal high flocculant and application thereof |
| CN103819023A (en) * | 2014-02-28 | 2014-05-28 | 金川集团股份有限公司 | Treatment and recycling method of industrial wastewater containing a plurality of heavy metal ions |
Non-Patent Citations (2)
| Title |
|---|
| 周全法等: "《废电脑及配件与材料的回收利用》", 31 August 2003, 化学工业出版社 * |
| 宋宏儒等: "高杂贵金属废水渣处理工艺的研究与应用", 《铜业工程》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114477507A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Treatment method and application of noble metal-containing production wastewater of vinyl acetate catalyst |
| CN114477507B (en) * | 2020-10-26 | 2023-05-23 | 中国石油化工股份有限公司 | Treatment method for waste water containing noble metal in vinyl acetate catalyst production and application thereof |
| CN112760488A (en) * | 2020-12-28 | 2021-05-07 | 格林美股份有限公司 | Separation method for iron in precious solution leached by automobile exhaust waste catalyst |
| CN114735842A (en) * | 2022-03-07 | 2022-07-12 | 金川集团股份有限公司 | Method for removing heavy metals from ammonia-containing wastewater |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102107978B (en) | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry | |
| CN102259996B (en) | Method for treating copper-containing waste water | |
| CN101628764B (en) | Processing method of industrial waste water generated in hydrometallurgical process of nickel, cobalt and copper | |
| CN102001734B (en) | Heavy metal settling agent for treating mercury-containing wastewater | |
| CN102775197B (en) | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board | |
| CN103482783A (en) | Treatment process for plumbic acid waste water generated in production process of lead storage batteries | |
| CN103436885A (en) | Method for recycling tin removal waste liquor | |
| CN103966446A (en) | Method for separating and recovering copper, nickel and iron from electroplating sludge | |
| CN109868476B (en) | Method for recycling etching liquid containing copper ions and nitrate radicals | |
| CN108529789B (en) | Method for treating copper-containing electroplating wastewater and recovering copper by using sulfide precipitation method | |
| CN102583819B (en) | Method for processing waste water generated by extracting copper oxide from acidic corrosion waste fluid | |
| CN109721187A (en) | A kind of chemical nickel plating waste solution processing method | |
| CN110484730A (en) | A method of recycling feed grade basic zinc chloride from zinc-containing sludge | |
| CN102417255B (en) | Efficient and economic mercury-containing waste water treatment method | |
| CN105293774A (en) | Method for increasing recovery rate of precious metals in waste liquid | |
| CN103214121B (en) | Method for recycling copper and iron in acid mine wastewater by high-polymer chelating-precipitating agent two-step process | |
| EP0922678A1 (en) | Waste treatment of metal plating solutions | |
| CN110790419B (en) | Method for treating electroless copper plating wastewater containing no hydroxyl-containing organic amine | |
| JP2004050096A (en) | Method for treating wastewater containing harmful substance without producing sludge, and chemical agent used therein | |
| CN103911513B (en) | Move back the treatment process of tin waste liquid | |
| CN113957248B (en) | Zinc-cobalt separation method for selective precipitation flotation of cobalt ions in acidic solution | |
| CN104692447B (en) | Etching waste liquor and wiring board mud are processed the method for preparing basic copper chloride simultaneously | |
| CN108002581B (en) | Method for cleaning high ammonia nitrogen wastewater containing metal ions | |
| CN112593233A (en) | Treatment method of printed circuit board etching waste liquid | |
| CN112374678A (en) | Treatment method of chemical nickel plating waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160203 |
|
| RJ01 | Rejection of invention patent application after publication |